EP0030804B1 - Crystalline 4,1',6'-trichloro-4,1',6'-trideoxy-galactosucrose - Google Patents

Crystalline 4,1',6'-trichloro-4,1',6'-trideoxy-galactosucrose Download PDF

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Publication number
EP0030804B1
EP0030804B1 EP80304259A EP80304259A EP0030804B1 EP 0030804 B1 EP0030804 B1 EP 0030804B1 EP 80304259 A EP80304259 A EP 80304259A EP 80304259 A EP80304259 A EP 80304259A EP 0030804 B1 EP0030804 B1 EP 0030804B1
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EP
European Patent Office
Prior art keywords
tgs
crystalline
water
trichloro
anhydrous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80304259A
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German (de)
English (en)
French (fr)
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EP0030804A1 (en
Inventor
Michael Ralph Jenner
David Waite
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Tate and Lyle PLC
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Tate and Lyle PLC
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Priority claimed from GB7943491A external-priority patent/GB2034323B/en
Application filed by Tate and Lyle PLC filed Critical Tate and Lyle PLC
Priority to AT80304259T priority Critical patent/ATE5076T1/de
Publication of EP0030804A1 publication Critical patent/EP0030804A1/en
Application granted granted Critical
Publication of EP0030804B1 publication Critical patent/EP0030804B1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
    • C07H5/02—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to halogen

Definitions

  • This invention relates to the carbohydrate sweetener 4,1',6'-trichloro-4,1',6'-trideoxygalacto- sucrose in a new form.
  • TGS 4,1',6'-Trichloro-4.,1',6'-trideoxyga/actosucrose, otherwise more properly known as 1,6-dichloro-1,6-dideoxy-/i-D-fructofuranosyl 4-chloro-4-deoxy-a-D-galactopyranoside, and hereinafter referred to as TGS, is a potent sweetening agent. Its use and compositions containing it are described and claimed in British Patent Specification No. 1 543 167. The compound itself was first reported by Fairclough, Hough and Richardson, Carbohydrate Research 40 (1975) 285-298, where it is described as syrup; but no sweet properties were ascribed to it.
  • the substance is obtainable by a reaction sequence in which sucrose is tritylated in positions 6,1' and 6', and acetylated in the remaining five positions.
  • the trityl groups are then removed with concurrent migration of the acetyl group on the 4-hydroxy group to the 6-hydroxy group.
  • the resulting 4,1',6'-triol pentaacetate is then chlorinated using sulphuryl chloride and de-acetylated to give TGS.
  • the product obtained in this way is a glass which is hygroscopic and which can be freeze-dried from an aqueous solution to give the glass as a fluffy white powder containing about 4% by weight of water.
  • TGS hygroscopic
  • TGS crystalline forms of TGS can be prepared which appear to be distinctly less hygroscopic than the glassy form.
  • Crystallisation was first achieved by seeding a concentrated aqueous solution of TGS (1 Og in 5ml) with an isomorphous crystalline substance which had been obtained by ion exchange resin treatment of an aqueous TGS solution.
  • the solution had been treated with a mixture of Amberlite (Trade Mark) IRA 35 and IRC 72 (weak anion and cation exchange resins), in order to remove sodium and chloride ions.
  • a fraction containing TGS as a syrup was obtained from the aqueous phase.
  • a later fraction was obtained by elution of the resin with methanol and this material crystallised.
  • a seed of this non-sweet, crystalline substance was used to seed a concentrated aqueous TGS solution.
  • the exact nature of the non-sweet crystalline substance is not known to us, but it is possibly an anhydro- sugar derived from TGS. All subsequent crystallisations were effected using crystalline TGS itself as seed.
  • the product obtained by crystallisation from water at room temperature over several hours was a clear crystalline form of TGS, m.p. 36.5°C, containing about 20% by weight of water (approximately 5.5 moles of water per mole). Crystallisation of the glass from water at 60°C gave a second clear crystalline form which was substantially anhydrous, containing 0.3-0.4% by weight of water, (approximately 0.07 to 0.09 moles of water per mole), m.p. 130°C. Crystallisation of the glass from undried methanol at 20°C gave another form, again as clear crystals, m.p. 120°C, containing 2.3% by weight of water (approximately 0.5 mole of water per mole) and approximately 0.4% methanol.
  • a curve of solubility against temperature for TGS in water is shown in the accompanying drawings as Figure 1.
  • a single discontinuity in the curve at about 38°C suggests the presence of effectively only two forms of TGS obtainable by crystallisation from water.
  • Our findings are that these are the pentahydrate, obtained by crystallisa.tion at temperatures below about 38°C, and the anhydrous form, obtained by crystallisation at temperatures above about 38°C, preferably above 60°C, e.g. about 70 ⁇ 80°C.
  • the pentahydrate can be dried in vacuo to remove some of its water of crystallisation to give various lower hydrates, but these appear only to consist of the pentahydrate structure with some water removed, rather than independent forms in their own right.
  • crystalline anhydrous 4,1',6'-trichloro-4,1',6'-trideoxyga/actosucrose and also crystalline 4,1',6'-trichloro-4,1',6'-trideoxyga/actosucrose pentahydrate, (C 12 H 19 O 8 Cl 3 . 5 H 2 O).
  • the compounds according to the present invention possess the same degree of sweetness as TGS in glass form and have the additional advantage of being considerably less hygroscopic, thus permitting easier handling and formulation.
  • the anhydrous form particularly, is very stable under humid conditions. Sorption isotherms for the anhydrous crystalline form and the glass show that the moisture adsorbed by the crystalline form is very much less than that adsorbed by the glass, which rapidly deliquesces at high humidities.
  • the anhydrous crystalline form is, in fact, remarkably similar to crystalline sucrose in its adsorption characteristics as may be seen from Figure 2 of the accompanying drawings which represents a plot of water content against ERH (equilibrium relative humidity) at 21 °C, using a NOVA-SINA equi-HYDROSCOPE humidity measuring instrument for the crystalline anhydrous form of TGS, sucrose and TGS glass (ascending curves).
  • ERH Equilibrium relative humidity
  • FIG. 3 in the accompanying drawings is a representation of the unit cell, based on X-ray crystallographic data.
  • the structure does not contain any suitable sites for water, and any small amounts of water in the substance are probably adsorbed on the surface of the crystals.
  • the following table contains the positional parameters (atomic coordinates) which were derived by X-ray crystallography on anhydrous crystalline TGS.
  • a saturated solution at 75°C has a solids content of about 73% while at 40° C the saturated solids content is about 39%.
  • a 1 OOg sample of a saturated solution at 75°C contains 27g of water and 73g of TGS. When this sample is cooled to 40°C, 27g of water remain, but in a solution with a solids content of 39% and a water content of 61 %. The solution thus contains 17.26g TGS, 55.74g of TGS having precipitated a yield of 76.35%. TGS can thus be crystallised in good yield from a sample water crystallisation above 40°C.
  • the pentahydrate may be obtained by crystallisation from water below 38°C.
  • a saturated solution at 35°C contains about 36% TGS, while at 10°C the content is only about 16% TGS, so a crystallisation will yield about 66% of TGS as the crystalline pentahydrate.
  • TGS is several hundred times sweeter than sucrose. The exact figure depends on the concentration of the sucrose solution with which a TGS solution is compared for equal sweetness. The following figures are typical:
  • the crystalline TGS can thus be used to sweeten all types of substances, including ingestible compositions (i.e. intended for consumption) and oral compositions (i.e. intended for oral application without swallowing, e.g. mouthwashes). It can be formulated, in particular, as a solid composition in association with a comestible carrier, diluent or exipient (e.g. in sweetening tablets etc) or with a foodstuff or beverage concentrate (e.g. a dry formulation for dilution with water to form a foodstuff, confection or beverage).
  • a comestible carrier diluent or exipient
  • a foodstuff or beverage concentrate e.g. a dry formulation for dilution with water to form a foodstuff, confection or beverage.
  • TGS was obtained by the method of Fairclough et al. (op. cit.)
  • a batch of 50g dissolved in hot acetone was chromatographed on a column of silica gel (600g), by elution with dichloromethane (1 litre) and gradient elution with dichloromethane/acetone (20 litres in all) to obtain a product showing only 1 spot on thin layer chromatography.
  • a further batch of 60g was treated similarly, and a total of 90g was obtained by combining the two yields.
  • This material was dissolved in water (10% concentration) and treated with about 1 OOg of a 50:50 mixture of Amberlite IRA 35 and IRC 72 resins for 1 hour with stirring.
  • TGS pentahydrate crystals were used to seed a hot saturated aqueous solution of TGS (about 60°) and this, on cooling, gave crystalline anhydrous TGS, m.p. 130°.
  • TGS pentaacetate (2.1 kg) obtained by the method of Fairclough et al. (op.cit) was deacetylated by treatment with methanolic sodium methoxide to give TGS as a syrup (ca. 1360g) which was dissolved in water (ca. 10%) and filtered through charcoal. The filtrate was concentrated to a syrup and redissolved in water at about 65% by weight. The solution was heated and seeded at about 65-70 0 with an authentic sample of crystalline TGS (anhydrous). The solution was cooled to 40° and then further to about ambient temperature. The crystalline material precipitated was filtered off.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Saccharide Compounds (AREA)
  • Seasonings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP80304259A 1979-12-18 1980-11-27 Crystalline 4,1',6'-trichloro-4,1',6'-trideoxy-galactosucrose Expired EP0030804B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80304259T ATE5076T1 (de) 1979-12-18 1980-11-27 Kristallin-4,1',6'-trichlor-4,1',6'-trideoxygalactosucrose.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB7943491A GB2034323B (en) 1978-12-18 1979-12-18 Production of dna comprising the b hepatitis viral genome
GB7943495 1979-12-18
GB8023819 1980-07-21
GB8023819 1980-07-21

Publications (2)

Publication Number Publication Date
EP0030804A1 EP0030804A1 (en) 1981-06-24
EP0030804B1 true EP0030804B1 (en) 1983-10-19

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ID=26273904

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EP80304259A Expired EP0030804B1 (en) 1979-12-18 1980-11-27 Crystalline 4,1',6'-trichloro-4,1',6'-trideoxy-galactosucrose

Country Status (17)

Country Link
US (1) US4343934A (enrdf_load_stackoverflow)
EP (1) EP0030804B1 (enrdf_load_stackoverflow)
AR (1) AR229023A1 (enrdf_load_stackoverflow)
AU (1) AU538458B2 (enrdf_load_stackoverflow)
CA (1) CA1154760A (enrdf_load_stackoverflow)
DE (1) DE3065399D1 (enrdf_load_stackoverflow)
DK (1) DK157196C (enrdf_load_stackoverflow)
ES (1) ES497862A0 (enrdf_load_stackoverflow)
FI (1) FI69470C (enrdf_load_stackoverflow)
GR (1) GR72757B (enrdf_load_stackoverflow)
IE (1) IE50634B1 (enrdf_load_stackoverflow)
IL (1) IL61667A (enrdf_load_stackoverflow)
NO (1) NO149242C (enrdf_load_stackoverflow)
NZ (1) NZ195867A (enrdf_load_stackoverflow)
PH (1) PH17320A (enrdf_load_stackoverflow)
PT (1) PT72207B (enrdf_load_stackoverflow)
YU (1) YU40784B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
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US7798993B2 (en) 1998-07-29 2010-09-21 Becton, Dickinson And Company Single use syringe

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US4435440A (en) * 1976-01-08 1984-03-06 Tate & Lyle Limited Sweeteners
CA1183133A (en) * 1980-10-28 1985-02-26 Tate & Lyle Public Limited Company Sweet chlorine-substituted disaccharides
DE3271880D1 (en) * 1981-04-29 1986-08-07 Tate & Lyle Plc Sweetening agents
ATE11544T1 (de) * 1981-05-22 1985-02-15 Tate & Lyle Public Limited Company Brom substituierte derivate von sucrose.
GB8500862D0 (en) * 1985-01-14 1985-02-20 Tate & Lyle Plc Composition
GB8525953D0 (en) * 1985-10-21 1985-11-27 Mcneilab Inc Preparation of galactopyranoside
GB8525954D0 (en) * 1985-10-21 1985-11-27 Mcneilab Inc Chlorination of carbohydrates &c alcohols
GB8617222D0 (en) * 1986-07-15 1986-08-20 Tate & Lyle Plc Sweetener
GB8627139D0 (en) * 1986-11-13 1986-12-10 Tate & Lyle Plc Sweetening composition
US4820528A (en) * 1987-03-27 1989-04-11 Nabisco Brands, Inc. Sweetener composition
KR890701026A (ko) * 1987-05-15 1989-12-19 원본 미기재 조절된 단맛을 가지는 추잉껌
US4986991A (en) * 1987-05-15 1991-01-22 Wm Wrigley, Jr., Company Chewing gum having an extended sweetness
US4950746A (en) * 1988-07-18 1990-08-21 Noramco, Inc. Process for synthesizing sucrose derivatives by regioselective reaction
US5169658A (en) * 1989-04-19 1992-12-08 Wm. Wrigley Jr. Company Polyvinyl acetate encapsulation of crystalline sucralose for use in chewing gum
US5059429A (en) * 1989-10-27 1991-10-22 Warner-Lambert Company Sucralose sweetened chewing gum
WO1990007859A2 (en) * 1989-11-22 1990-07-26 Wm. Wrigley Jr. Company Method of controlling release of sucralose in chewing gum and gum produced thereby
US5059428A (en) * 1990-03-12 1991-10-22 Warner-Lambert Company Synergistic sweetening compositions containing polydextrose and a chlorodeoxysurgar and methods for preparing same
US5089608A (en) * 1990-03-23 1992-02-18 Mcneil-Ppc, Inc. Selective 6-acylation of sucrose mediated by cyclic adducts of dialkyltin oxides and diols
US5023329A (en) * 1990-04-23 1991-06-11 Noramco, Inc. Sucrose-6-ester production process
US5139798A (en) * 1990-11-21 1992-08-18 Wm. Wrigley Jr. Company Polyvinyl acetate encapsulation of codried sucralose for use in chewing gum
NZ240818A (en) 1990-12-14 1993-08-26 Mcneil Ppc Inc Liquid sucralose concentrate compositions containing preservative, buffer and liquid
US5169657A (en) * 1991-07-17 1992-12-08 Wm. Wrigley Jr. Company Polyvinyl acetate encapsulation of sucralose from solutions for use in chewing gum
US5747091A (en) * 1992-03-30 1998-05-05 Tate & Lyle Public Limited Company Sweetened extruded food products
GB9517281D0 (en) * 1995-08-23 1995-10-25 Tate & Lyle Plc Solid sucralose
US8202257B2 (en) 1998-07-29 2012-06-19 Becton, Dickinson And Company Splatter prevention mechanism for a syringe
US6322774B1 (en) 1999-12-20 2001-11-27 Ultradent Products, Inc. Dental bleaching compositions containing sucralose
US6312671B1 (en) 1999-12-20 2001-11-06 Ultradent Products, Inc. Dental bleaching compositions containing sucralose
BR0115482B1 (pt) * 2000-11-17 2013-02-19 sacralose cristalina, seu processo de cristalizaÇço e seu produto.
US8263150B2 (en) 2001-12-19 2012-09-11 The Procter & Gamble Company Beverage compositions having low levels of preservative with enhanced microbial stability
US6998480B2 (en) 2002-03-08 2006-02-14 Tate & Lyle Public Limited Company Process for improving sucralose purity and yield
US7049435B2 (en) 2002-03-08 2006-05-23 Tate & Lyle Public Limited Company Extractive methods for purifying sucralose
US20040170735A2 (en) * 2002-04-05 2004-09-02 Mcneil-Ppc, Inc. Methods and compositions for altering the sweetness delivery profile of sucralose
US6943248B2 (en) * 2003-04-30 2005-09-13 Tate & Lyle Public Limited Company Crystalline form of sucralose, and method for producing it
EA200601742A1 (ru) * 2004-03-19 2007-02-27 Фармед Медикэр Прайвит Лимитед Усовершенствованный способ производства хлорированной сахарозы
US20050214425A1 (en) * 2004-03-23 2005-09-29 Roma Vazirani Sugar substitute prepared with nutritive and high-intensity sweeteners
WO2006011301A1 (ja) * 2004-07-29 2006-02-02 Ensuiko Sugar Refining Co., Ltd. 結晶ラクトスクロースまたはそれを含有する含蜜結晶とその用途
US20060247180A1 (en) * 2005-04-29 2006-11-02 Bergey James L Purgative composition and uses thereof
CN100567319C (zh) * 2006-07-12 2009-12-09 上海迪赛诺维生素有限公司 一种三氯蔗糖的结晶方法
US8575333B2 (en) * 2006-09-14 2013-11-05 Bahram Memarzadeh Halogenated alkyl di- and trisaccharides, pharmaceutical formulations, diagnostic kits and methods of treatment
CN100591684C (zh) * 2006-12-27 2010-02-24 盐城捷康三氯蔗糖制造有限公司 三氯蔗糖结晶方法
CN101260126B (zh) * 2007-03-06 2010-12-22 盐城捷康三氯蔗糖制造有限公司 三氯蔗糖的结晶方法
CN101245085B (zh) 2007-12-19 2012-02-01 上海同辰生物科技有限公司 一种三氯蔗糖的合成及纯化工艺
WO2009108842A1 (en) * 2008-02-29 2009-09-03 Tate & Lyle Technology Ltd Agglomerates of sucralose and polyols, and their use in chewing gums
CN102336786A (zh) * 2011-11-01 2012-02-01 安徽万和制药有限公司 一种三氯蔗糖的高效结晶方法
CN103242384B (zh) * 2013-05-27 2015-12-02 南通市常海食品添加剂有限公司 三氯蔗糖母液萃取工艺

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US3978678A (en) * 1975-10-14 1976-09-07 Hydrotech International, Inc. Method and apparatus for plugging a pipeline
GB1543167A (en) * 1976-01-08 1979-03-28 Tate & Lyle Ltd Sweeteners
IL58275A0 (en) * 1978-09-22 1979-12-30 Tate & Lyle Patent Holdings Compositions for prevention of tooth decay comprising chlorodeoxysucrose derivative

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7798993B2 (en) 1998-07-29 2010-09-21 Becton, Dickinson And Company Single use syringe

Also Published As

Publication number Publication date
DE3065399D1 (en) 1983-11-24
NO803848L (no) 1981-06-19
ES8204484A1 (es) 1982-05-01
ES497862A0 (es) 1982-05-01
CA1154760A (en) 1983-10-04
DK157196B (da) 1989-11-20
NZ195867A (en) 1982-11-23
IL61667A (en) 1984-05-31
YU316980A (en) 1983-12-31
FI69470B (fi) 1985-10-31
IL61667A0 (en) 1981-01-30
AU6515180A (en) 1981-06-25
FI803959L (fi) 1981-06-19
YU40784B (en) 1986-06-30
DK157196C (da) 1990-04-23
FI69470C (fi) 1986-02-10
EP0030804A1 (en) 1981-06-24
IE50634B1 (en) 1986-05-28
PT72207B (en) 1981-10-28
DK537880A (da) 1981-06-19
US4343934A (en) 1982-08-10
IE802658L (en) 1981-06-18
NO149242C (no) 1984-03-14
PT72207A (en) 1981-01-01
PH17320A (en) 1984-07-20
NO149242B (no) 1983-12-05
GR72757B (enrdf_load_stackoverflow) 1983-12-02
AR229023A1 (es) 1983-05-31
AU538458B2 (en) 1984-08-16

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